Red emitting nanofibers, KGdTa2O7:Eu3+ were synthesized by electrospinning technique followed by heat treatment. As-prepared uniform fiber precursor with diameter ranging from about 700 nm to about 900 nm were calcined after removing organic species by calcination. The fiber surface become rough and diameter decreased to about 250-340 nm range due to decomposition of organic species and formation of inorganic phase. Morphology, structural and photoluminescent properties of fibers were analyzed using thermogravimetric and differential thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL). TG-DTA analysis indicates that KGdTa2O7:Eu3+ began to crystalize at 520 degrees C. Fibers annealed at 900 degrees C formed well crystallized uniform fibers. Under ultraviolet excitation KGdTa2O7:Eu3+ exhibits red emission due to transitions in 4f states of Eu3. The excitation band is dominated by the Eu3+-O2- charge transfer band peaked at 289 nm. The emission peak is in the region that is ideal for red light emission.